This invention pertains to certain novel colorant compounds which contain one or more ethylenically-unsaturated (vinyl), photopolymerizable radicals which may be copolymerized (or cured) with ethylenically-unsaturated monomers to produce colored compositions such as colored acrylic polymers, e.g., polymers produced from acrylate and methacrylate esters, colored polystyrenes, and similar colored polymeric materials derived from other ethylenically-unsaturated monomers. The present invention also pertains to processes for preparing certain of the photopolymerizable colorant compounds.
It is known (J.S.D.C., April 1977, pp 114-125) to produce colored polymeric materials by combining a reactive polymer such terepolymers having epoxy groups or polyacryloyl chloride with anthraquinone dyes containing nucleophilic reactive groups such as amino or hydroxy groups; to graft acryloylaminoanthraquinone dyes to the backbone of vinyl or divinyl polymers; and to polymerize anthraquinone dyes containing certain olefinic groups to produce polymeric dyes/pigments. U.S. Pat. No. 4,115,056 describes the preparation of blue, substituted 1,4-diaminoanthraquinone dyes containing one acryloyloxy group and and the use of the dyes in coloring various fibers, especially polyamide fibers. U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymers containing certain blue, substituted 1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic group copolymerized therein to provide liquid crystal copolymers having high dichromism. U.S. Pat. No. 5,055,602 describes the preparation of certain substituted 1,4-diaminoanthraquinone dyes containing polymerizable acryloyl and methacryloyl groups and their use in coloring polyacrylate contact lens materials by copolymerizing.
U.S. Pat. No. 5,362,812 discloses the conversion of a variety of dye classes, including anthraquinones, into polymeric dyes by (a) polymerizing 2-alkenylazlactones and reacting the polymer with dyes containing nucleophilic groups and by (b) reacting a nucleophilic dye with an alkenylazlactone and then polymerizing the free radically polymerizable dyes thus produced. The polymeric dyes are reported to be useful for photoresist systems and for colorproofing. U.S. Pat. No. 5,367,039 discloses a process for preparing colored vinyl polymers suitable for inks, paints, toners and the like by emulsion polymerization of a vinyl monomer with reactive anthraquinone dyes prepared by functionalizing certain anthraquinone dyes with methacryloyl groups.
The preparation of a variety of dyes, including some anthraquinones, which contain photopolymerizable groups and their use for color filters suitable for use in liquid crystal television sets, color copying machines, photosensitive resist resin compositions, and the like are described in U.S. Pat. No. 5,578,419.
The first embodiment of the present invention concerns colorant compounds having Formulas I and II: 
wherein
A, is a mono-, di-, tri- or tetravalent chromophore;
X is xe2x80x94R1xe2x80x94Oxe2x80x94Q or the phtopolymerizable group xe2x80x94CH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2;
Y is xe2x80x94R1xe2x80x94Oxe2x80x94Q, xe2x80x94CH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2 or Q;
R is selected from hydrogen, C1-C6 alkyl, aryl and C3-C8 cycloalkyl;
R1 is selected from C2-C8 alkylene, xe2x80x94(xe2x80x94CH2CH2Oxe2x80x94)mxe2x80x94CH2CH2xe2x80x94 and 1,4-cyclohexylenedimethylene;
R2 is selected from hydrogen and C1-C6 alkyl;
n is 1 to 4;
m is 1-3;
Q is a photopolymerizable group selected from an organic radical having the formulae:
xe2x80x94COC(R3)xe2x95x90CHxe2x80x94R1xe2x80x83xe2x80x83Ia
xe2x80x94CONHCOC(R3)xe2x95x90CHxe2x80x94R4xe2x80x83xe2x80x83IIa
xe2x80x94CONHxe2x80x94C1-C6-alkylene OCOC(R3)xe2x95x90CHxe2x80x94R4xe2x80x83xe2x80x83IIIa

xe2x80x83wherein
R3 is selected from hydrogen or C1-C6 alkyl;
R4 is selected from hydrogen; C1-C6alkyl; phenyl; phenyl substituted with one or more groups selected from C1-C6 alkyl, C1-C6 alkoxy, xe2x80x94N(C1-C6 alkyl)2, nitro, cyano, C2-C6 alkoxycarbonyl, C2-C6 alkanoyloxy and halogen; 1- and 2-naphthyl; 1- and 2-naphthyl substituted with C1-C6 alkyl or C1-C6 alkoxy; 2- and 3-thienyl; 2- and 3-thienyl substituted with C1-C6 alkyl or halogen; 2- and 3-furyl; and 2- and 3-furyl substituted with C1-C6 alkyl;
R5 and R6 are independently selected from hydrogen, C1-C6 alkyl, substituted C1-C6 alkyl; aryl; or R5 and R6 may be combined to represent a xe2x80x94(xe2x80x94CH2xe2x80x94)3-5xe2x80x94 radical;
R7 is selected from hydrogen or a group selected from C1-C6 alkyl, substituted C1-C6 alkyl, C3-C8 alkenyl, C3-C8 cycloalkyl and aryl; and
R8 is selected from hydrogen, C1-C6 alkyl and aryl. The colorant compounds have good color strength, good solubility in the reactive monomers and good light-fastness. Certain of the colorant compounds exhibit outstanding thermal stability.
A second embodiment of the present invention concerns a process for preparing photopolymerizable colorants having Formula I, wherein X is a p-vinylbenzyl radical having the formula xe2x80x94CH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2 which comprises reacting colored acidic compounds having the structure:
xe2x80x83A"Parenopenst"CO2xe2x80x94H)n
with the compounds having the structure ClCH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2 in the presence of base, wherein A, R2 and n are as defined previously.
A third embodiment of the present invention concerns a process for preparing photopolymerization colorants having Formula II, wherein Y is a p-vinylbenzyl radical having the formula xe2x80x94CH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2 which comprises reacting colored acidic compounds having the structure 
with 4-chloromethylstyrene compounds having the structure ClCH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2 in the presence of a base, wherein A, R, R2 and n are defined above.
A fourth embodiment of the invention concerns a process for preparing colored photopolymerizable compounds having Formula I and Formula II, respectively, wherein X and Y are xe2x80x94CH2CH2xe2x80x94Oxe2x80x94Q or xe2x80x94CH2CH(CH3)xe2x80x94Oxe2x80x94Q, which comprises the steps of
(a) reacting a colored acidic compounds having the structures: 
xe2x80x83respectively, with at least about n molecular equivalents of ethylene or propylene carbonate for each molecular equivalent of acidic compounds to produce the 2-hydroxyalkyl derivatives of said acidic compounds followed by:
(b) reaction of said colored hydroxyalkyl derivatives with about n molecular equivalents of one or more acylating agents having the structures
xe2x80x83ClCOC(R3)xe2x95x90CHxe2x80x94R4 or O[COC(R3)xe2x95x90CHxe2x80x94R4]2,xe2x80x83xe2x80x83Ib
Oxe2x95x90Cxe2x95x90Nxe2x80x94COC(R3)xe2x95x90CHxe2x80x94R4,xe2x80x83xe2x80x83IIb
Oxe2x95x90Cxe2x95x90Nxe2x80x94C1-C6 alkylene OCOC(R3)xe2x95x90CHxe2x80x94R4,xe2x80x83xe2x80x83IIIb

wherein A, n, Q, R, R3, R4, R5, R6, R8 are defined previously.
A fifth embodiment of the present invention concerns a process for preparing compounds of Structure II wherein Y is a photopolymerizable group Q which comprises reacting colored acidic compounds having the structure: 
with at least about n molecular equivalents of one or more acylating agents Ib through IXb described above wherein A, R, n and Q are defined above.
A sixth embodiment of the present invention pertains to a coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the colorant compounds having Formulas I and II described above, and (iii) a photoinitiator. A seventh embodiment of the present invention pertains to a polymeric composition, typically a coating, comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other polymerizable vinyl compounds, having copolymerized therein one or more of the colorant compounds having Formulas I and II described above.
In formulas I and II, A represents a mono-, di-, tri- or tetravalent residue of a chromophore, i.e., a colored compound, including residues which in combination with xe2x80x94CO2X produces a chromophore. Examples of the chromophoric residues which A may represent include anthraquinone, anthrapyridone (3H-dibenz-[f,ij]-isoquinoline-2,7-dione, anthrapyrimidine (7H-dibenz-[f,ij]-isoquinoline-7-one), anthrapyrimidine (7H-benzo[e]-perimidine-7-one), anthrapyrimidone, isothiazoloanthrone, azo, bis-azo, methine, bis-methine, coumarin (2-H-1-benzopyran-2-one), 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxypyrroline, perinone, quinophthalone, phthalocyanine, metal phthalocyanine, nitroarylamine or a 2,5-diarylaminoterephthalic ester chromophore.
The terms xe2x80x9cC1-C6-alkylxe2x80x9d and xe2x80x9cC1-C8-alkylxe2x80x9d are used herein to denote a straight- or branched-chain, saturated, aliphatic hydrocarbon radical containing one to six, and one to eight, carbon atoms. The term xe2x80x9csubstituted C1-C6-alkylxe2x80x9d is used to denote a C1-C6-alkyl group substituted with one or more groups, preferably one to three groups, selected from the group consisting of hydroxy, halogen, cyano, aryl, aryloxy, arylthio, C1-C6 alkylthio, C3-C8-cycloalkyl, C2-C6-alkanoyloxy and xe2x80x94(xe2x80x94Oxe2x80x94R9xe2x80x94)pxe2x80x94R10 wherein R9 is selected from the group consisting of C1-C6 alkylene, C1-C6-alkylene-arylene, cyclohexylene, arylene, C1-C6-alkylene-cyclohexylene and C1-C6-alkylene-cyclohexylene-C1-C6-alkylene, R10 is selected from the group consisting of hydrogen, hydroxy, carboxy, C2-C6-alkanoyloxy, C2-C6-alkoxycarbonyl, aryl and C3-C8-cycloalkyl; and p is 1, 2, or 3.
The terms xe2x80x9cC1-C6-alkylenexe2x80x9d, xe2x80x9cC2-C4-alkylenexe2x80x9d and xe2x80x9cC2-C8-alkylenexe2x80x9d are used to denote straight- or branched-chain, divalent, aliphatic hydrocarbon radicals containing one to six, two to four, and two to eight carbons, respectively. These divalent radicals may be substituted with one to three groups selected from C1-C6-alkoxy, C2-C6-alkoxycarbonyl, C2-C6-alkanoyloxy, hydroxy, aryl and halogen. The term xe2x80x9cC3-C8-alkenylxe2x80x9d is used to denote an aliphatic hydrocarbon radical containing at least one double bond. The term xe2x80x9cC3-C8-alkynylxe2x80x9d is used to denote an aliphatic hydrocarbon radical containing at least one triple bond and three to eight carbon atoms. The term xe2x80x9cC3-C8-cycloalkylxe2x80x9d is used to denote a saturated, carbocyclic, hydrocarbon radical having three to eight carbon optionally substituted with one to three C1-C6-alkyl group(s). The term xe2x80x9cC3-C8-cycloalkylenexe2x80x9d is used to denote a divalent, carbocyclic hydrocarbon radical which contains three to eight carbon atoms, preferably five or six carbons.
The term xe2x80x9carylxe2x80x9d as used herein denotes phenyl and phenyl substituted with one to three substituents selected from C1-C6-alkyl, substituted C1-C6-alkyl, C1-C6-alkoxy, halogen, carboxy, cyano, C2-C6-alkanoyloxy, C1-C6-alkylthio, C1-C6-alkylsulfonyl, trifluoromethyl, hydroxy, optionally substituted sulfamoyl, C2-C6-alkoxycarbonyl, C2-C6-alkanoyl-amino and xe2x80x94Oxe2x80x94R11, Sxe2x80x94R11, xe2x80x94SO2xe2x80x94R11, xe2x80x94NHSO2R11 and xe2x80x94NHCO2R11, wherein R11 is phenyl or phenyl substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen. The term xe2x80x9carylenexe2x80x9d as used herein denotes includes 1,2-, 1,3- and 1,4-phenylene and such divalent radicals substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen.
The term xe2x80x9chalogenxe2x80x9d is used to include fluorine, chlorine, bromine, and iodine. The term xe2x80x9coptionally substituted sulfamoylxe2x80x9d is used to describe the group having the structure xe2x80x94SO2N(R12)R13, wherein R12 and R13 are independently selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl and heteroaryl.
The terms xe2x80x9cC1-C6-alkoxyxe2x80x9d, xe2x80x9cC2-C6-alkoxycarbonylxe2x80x9d, xe2x80x9cC2-C6-alkanoylxe2x80x9d, xe2x80x9cC2-C6-alkanoyloxyxe2x80x9d and xe2x80x9cC2-C6-alkanoylaminoxe2x80x9d are used to denote radicals corresponding to the structures xe2x80x94OR14, xe2x80x94CO2 R14, xe2x80x94COR14, xe2x80x94OCOR14 and NHCOR14, respectively, wherein R14 is C1-C6-alkyl or substituted C1-C6-alkyl. The term xe2x80x9cheteroarylxe2x80x9d as used herein denotes a 5- or 6-membered aromatic ring containing one to three hetero atom selected from oxygen, sulfur and nitrogen. Examples of such heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl, benzoxazolyl, benothiazolyl, benzimidazolyl, indolyl and the like and these optionally substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy, substituted C1-C6-alkyl, halogen, C1-C6-alkylthio, aryl, arylthio, aryloxy, C2-C6-alkoxycarbonyl and C2-C6-alkanoylamino.
The preferred azo dyes of the invention encompassed by Formula I have the following general Formula XIII:
Dxe2x80x94Nxe2x95x90Nxe2x80x94Zxe2x80x83xe2x80x83XIII
wherein D is the residue of an aromatic or heteroaromatic, diazotizable amine which has been diazotized and coupled with an electron rich coupling component Hxe2x80x94Z and is preferably derived from the aromatic and heteroaromatic classes of unsubstituted and substituted anilines, 1-naphthylamines, 1-aminoanthraquinones, 4-aminoazobenzenes, 2-aminothiazoles, 2-aminobenzothiazoles, 3-amino-2,1-benzisothiazoles, 2-aminothieno [2,3-d]thiazoles, 5-aminopyrazoles, 4-aminopyrazoloisothiazoles, 2-amino-1,3,4-thiadiazoles, 5-amino-1,2,3-thiadiazoles, 5-amino-1,2,3-triazoles, 2-amino-1,3,4-triazoles, 2(5)aminoimidazoles, 3-aminopyridines, 2(3)aminothiophenes, 2(3)aminobenzo [5]thiophenes, 2-aminothieno[3,2-5]thiophenes, 3-aminothieno[2,3]-isothiazoles, 3-amino-7-benz-2,1-isothiazoles, 3-aminoisothiazolo[3,4-d]pyridines, 3(4)-aminophthalimides and 5(6)amino-1,2-benzisothiazolon-1, 1-dioxides; wherein the substituents which are present on D are selected from C1-C6-alkyl; C1-C6-alkoxy; C3-C8-cycloalkyl; halogen; C2-C6-alkoxycarbonyl; 
C2-C6-alkanoyloxy; formyl; C2-C6-alkanoyl; dicyanovinyl; thiocyano; trifluoro-methyl; trifluoroacetyl; cyano; carbamoyl; xe2x80x94CONHC1-C6-alkyl; xe2x80x94CON(C1-C6-alkyl)2; xe2x80x94CONH aryl; sulfamoyl; xe2x80x94SO2NHC1-C6-alkyl; xe2x80x94SO2N(C1-C6-alkyl)2; xe2x80x94SO2NHaryl; xe2x80x94SO2NHC3-C8-cycloalkyl; xe2x80x94CONHC3-C8-cycloalkyl; aryl; aroyl; heteroaryl; NHSO2C1-C6 alkyl; N(C1-C6-alkyl) SO2C1-C6-alkyl; NHSO2 aryl; NHCO2C1-C6-alkyl; NHCONH C1-C6-alkyl; NHCONH aryl; xe2x80x94Nxe2x80x94(C1-C6-alkyl)-aryl; arylazo; aryloxy; arylthio; C3-C8-cycloalkoxy; heteroarylazo; heteroarylthio; arylsulfonyl; tricyanovinyl; aryloxysulfonyl; C1-C6-alkylsulfonyl; fluorosulfonyl; trifluoromethylsulfonyl; hydroxy; nitro and xe2x80x94CHxe2x95x90AM, wherein AM is the residue of an active methylene compound; xe2x80x94CO2X and 
wherein xe2x80x94Lxe2x80x94 is a linking group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and xe2x80x94SO2xe2x80x94 and X is as defined previously; Z is the residue of an electron rich coupling component selected from the classes of anilines, 1,2,3,4-tetrahydroquinolines, aminonaphthylamines, benzomorpholines (3,4-dihydro-2H-1,4-benzoxazines), pyrazolones, pyrazoles, 3-cyano-6-hydroxy-2-pyridones, 2,3-dihydroindoles, indoles, 4-hydroxycoumarins, 4-hydroxy-2-quinolones, imidazo[2,1-b]-thiazoles, 2,6-diamino-3-cyanopyridines; 5,5-dimethyl-1,3-cyclohexanedione(dimedone), phenols, naphthols and 2,4-pentanediones; wherein the azo compounds of Formula XIII contain a total of from one to four photopolymerizable groups (xe2x80x94CO2X), wherein said group(s) may be positioned on moiety D and/or moiety Z.
Another group of preferred azo dye of the invention encompassed by Formula II have the general Formula XIV:
D1-Nxe2x95x90Nxe2x80x94Z1xe2x80x83xe2x80x83XIV
wherein D1 is the residue of an aromatic or hereroaromatic amine which has been diazotized and coupled with an electron rich coupling component HZ1, wherein D1 is derived from the same optionally substituted aromatic amines and heteroaromatic amines as described for Formula XIII above, except that the photopolymerizable group which may be present on D1, is a triazolyl radical having the formula: 
instead of xe2x80x94CO2X or 
and wherein R and Y are as previously defined; Z1 is the residue of a coupling component selected from the same classes as described above for Z in Formula XIII and which may be substituted with the group 
with the provision that the azo compounds of Formula XIV contain a total of from one to four photopolymerizable groups 
wherein said groups(s) may be positioned on moiety D1 and/or moiety Z1.
Typical coupler residues represented by Z above in Formula XIII include the groups having the structures: 
wherein R15 is hydrogen or 1-2 groups selected from C1-C6-alkyl, C1-C6-alkoxy, halogen, NHCOR22, NHCO2R22, NHCON(R22) R23 and NHSO2R23, wherein R22 is selected from hydrogen, C1-C6-alkyl, C3-C8-cycloalkyl and aryl, R23 is selected from C1-C5-alkyl, C3-C8-cycloalkyl and aryl, wherein each C1-C6 alkyl group in R22 and R23 may be further substituted with one or more groups selected from C1-C6-alkoxy, hydroxy, C3-C8-cycloalkyl, aryl, aryloxy, arylthio, cyano, succinimido, xe2x80x94CO2X, 
wherein xe2x80x94CO2X is a photopolymerizable group as described above; L1 is selected from a covalent bond, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CO2xe2x80x94, xe2x80x94SO2NHxe2x80x94, xe2x80x94CONHxe2x80x94and xe2x80x94SO2N(C1-C6-alkyl)xe2x80x94; wherein each aryl group in R22 and R23 in the definition of R15 may be substituted with at least one photopolymerizable xe2x80x94CO2X group; wherein R24 represents hydrogen or 1-2 groups selected from xe2x80x94CO2X, C1-C6-alkyl, C1-C6-alkoxy and halogen; R16 and R17 are independently selected from hydrogen; C3-C8-cycloalkyl; C3-C8-alkenyl; C3-C8-alkynyl; C1-C6-alkyl and C1-C6-alkyl substituted with one or more groups selected from xe2x80x94CO2X, 
C3-C8-cycloalkyl, aryl, hydroxy, cyano, xe2x80x94OC2H4OH, xe2x80x94SCH2CH2OH, halogen, xe2x80x94OC1-C6-alkyl, xe2x80x94SC1-C6-alkyl, xe2x80x94O aryl, xe2x80x94S aryl, xe2x80x94SO2 aryl, xe2x80x94SO2C1-C6-alkyl, xe2x80x94S heteroaryl, 2-pyrrolidino, phthalimidino, phthalimdo, succinimido, glutarimido, o-benzoic sulfimido, xe2x80x94NHCOC1-C6-alkyl, xe2x80x94NHCOH, xe2x80x94NHSO2 C1-C6-alkyl, xe2x80x94NHSO2aryl, xe2x80x94NHCOaryl, xe2x80x94NHCO2C1-C6-alkyl, xe2x80x94SO2NH2, xe2x80x94CONH2, xe2x80x94SO2NHxe2x80x94C1-C6-alkyl, xe2x80x94SO2N(C1-C6-alkyl)2, xe2x80x94CO2C1-C6-alkyl, xe2x80x94CONH C1-C6-alkyl, xe2x80x94CO2-aryl, xe2x80x94CON-(C1-C6-alkyl)2, xe2x80x94CONH-aryl, xe2x80x94CONxe2x80x94(C1-C6-alkyl)aryl, xe2x80x94SO2N(C1-C6-alkyl)aryl, xe2x80x94OCOC1-C6-alkyl, xe2x80x94OCOaryl, xe2x80x94OCO2C1-C6-alkyl; groups of the formulae: 
wherein Y2 is selected from 1,2-phenylene; 1,2-phenylene substituted with C1-C6 alkyl, C1-C6-alkoxy, halogen, CO2C1-C6-alkyl or nitro; C2-C4 alkylene; xe2x80x94OCH2xe2x80x94; xe2x80x94SCH2xe2x80x94; xe2x80x94CH2OCH2xe2x80x94; xe2x80x94CH2SCH2xe2x80x94; xe2x80x94NHCH2xe2x80x94; xe2x80x94NHCH2CH2xe2x80x94N(C1-C6-alkyl)CH2xe2x80x94; xe2x80x94N(C1-C6-alkyl)CH2CH2; xe2x80x94NHC(aryl)2, and wherein R16 and R17 may be combined with themselves or another element to which they are attached to form a radical Z having the formula: 
wherein L3 is selected from a covalent bond, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94CH2xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94N(COC1-C6-alkyl)xe2x80x94, xe2x80x94N(SO2C1-C6-alkyl)xe2x80x94, xe2x80x94N(COaryl)xe2x80x94 and xe2x80x94N(SO2aryl)xe2x80x94; R18, R19 and R20 are independently selected from hydrogen and C1-C6-alkyl; R21 is selected from hydrogen, C1-C6-alkyl and aryl.
Typical coupler residue represented by Z1 is Formula XIV include those mentioned immediately above Z except that the photopolymerizable group which may be present as a substituent or on R15, R16, R17, R22, or R23 is the triazolyl group having the formula: 
instead of those listed.
The preferred methine, bis-methine, 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxypyrroline and coumarin compounds of Formula I have the following general Formulas XV, XVI, XVII, XVIII and XIX respectively;
R25xe2x80x94CHxe2x95x90AMxe2x80x83xe2x80x83XV
R25xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90AMxe2x80x83xe2x80x83XVI

wherein R25 is an electron rich aromatic residue selected from the following: 
wherein R16, R17, R18, R19, R20 and R21 are as defined for Z previously in Formula XIII; wherein R16xe2x80x2 is selected from the same groups as R16; wherein R26 is selected from cyano, C1-C6-alkoxycarbonyl, C1-C6-alkylsulfonyl, arylsulfonyl, aryl, heteroaryl, formyl, C1-C6-alkanoyl or xe2x80x94CHxe2x95x90AM; wherein R27 is hydrogen or cyano; wherein AM is the residue of an active methylene compound selected from malononitrile, xcex1-cyanoaceticacid esters, malonic acid esters, xcex1-cyanoacetic acid amides, xcex1-C1-C6-alkylsulfonyl-acetonitriles, xcex1-arylsulfonylacetonitriles, xcex1-C1-C6-alkanoylacetonitriles, xcex1-arylsulfonylacetonitriles, xcex1-C1-C6-alkanoylacetonitriles, xcex1-arylacetonitriles, xcex1-hereroacylacetonitriles, bis(heteroaryl) methanes, 1,3-indanediones, 2-furanones, benzo-2-furanones, benzo (b) thieno-3-xlidene propanedinitrile-5,5-dioxides, 1,3-bis(dicyanomethylene)indanes, barbituric acid, 5-pyrazolones, dimedone, 3-oxo-2,3-dihydro-1-benzothiophene-1,1-dioxides, aryl C(CH3)xe2x95x90C(CN)2 and NC CH2 CO2X, R28; wherein xe2x80x94CO2X is a photopolymerizable group as previously defined.
Examples of the anthraquinone (Formulas XXa-e), anthrapyridone (3H-dibenz-[f,ij]-isoquinoline-2-7-dione) (Formulas XXI a-e) and anthrapyridine (7H-dibenz-[f,ij]-isoquinoline-7-one) (Formulas XXII a-e) colorants include the compounds having the structures set forth below: 
wherein R28 is hydrogen or represents 1-4 groups selected from amino; C1-C8-alkylamino; C1-C8-alkylamino substituted with one or more groups selected from hydroxy, cyano, halogen, aryl, heteroaryl, C3-C8-cycloalkyl, furyl, C1-C6-alkoxy, C1-C6-alkylthio, arylthio, aryloxy, xe2x80x94(OCH2CH2xe2x80x94)1-3ORxe2x80x2, wherein Rxe2x80x2 is selected from hydrogen, C1-C6-alkyl and C2-C6-alkanoyloxy; C3-C8-cycloalkylamino; C3-C8-alkenylamino; C3-C8-alkynylamino; arylamino; furfurylamino; C1-C6-alkoxy; xe2x80x94(OCH2CH2xe2x80x94)1-3ORxe2x80x2, wherein Rxe2x80x2 is as defined previously; halogen; hydroxy; C1-C6-alkylthio; arylthio; aryl; aryloxy; arylsulfonyl C2-C6-alkanoyl; aroyl; C2-C6-alkanoyloxy; C2-C6-alkoxycarbonyl; heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano; xe2x80x94SO2C1-C6-alkyl; xe2x80x94SO2NH2; xe2x80x94SO2NHC1-C6-alkyl; xe2x80x94SO2N(C1-C6alkyl)2; xe2x80x94SO2N(C1-C6alkyl)aryl; xe2x80x94SO2NHaryl; xe2x80x94CONH2; CONHC1-C6-alkyl; xe2x80x94CON(C1-C6-alkyl)2; xe2x80x94CONHaryl; xe2x80x94CON(C1-C6-alkyl)aryl; C1-C6-alkyl; tetrahydrofurfurylamino; 4-(hydroxymethyl)cyclohexylmethylamino; and 
R29 is hydrogen or 1-2 groups selected from C1-C6-alkyl, halogen and C1-C6-alkoxy; R30 is selected from hydrogen, C1-C8-alkyl, substituted C1-C8-alkyl as defined previously in the definition of R28, aryl and C3-C8-cycloalkyl; R31 is selected from hydrogen, cyano, C1-C6-alkoxy, C1-C6-alkylthio, aryl, aryloxy, arylamino, arylthio, heteroaryl, heteroarylthio, halogen, C2-C6-alkoxycarbonyl, aroyl; C1-C6-alkylsulfonyl, arylsulfonyl and C1-C6-alkylamino; R32 is selected from hydrogen, C1-C6-alkyl, aryl and xe2x80x94N(R33)R34, wherein R33 and R34 are independently selected from hydrogen; C1-C6-alkyl; C1-C6-alkyl substituted with C2-C6-alkanoyloxy, aryl and C3-C8-cycloalkyl; aryl; C3-C8-cycloalkyl; wherein R33 and R34 may be combined to produce divalent radicals such as xe2x80x94(CH2)xe2x80x944-6 and xe2x80x94CH2CH2xe2x80x94L6xe2x80x94CH2CH2xe2x80x94, wherein L6 is selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94and xe2x80x94N(R34)xe2x80x94, wherein R34xe2x80x2 is selected from hydrogen, C1-C6-alkyl, aryl, aroyl, C1-C6-alkanoyl, C1-C6-alkylsulfonyl and aryl-sulfonyl; L4 and L5 are selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CON(R33)xe2x80x94and xe2x80x94SO2N(R33)xe2x80x94.
Some of the preferred colorants encompassed by Formula I wherein A is a quinophthalone chromophore have the following Formula XXIII: 
wherein R35 is selected from hydrogen, bromine, arylthio, heteroarylthio, arylsulfonyl, 
wherein X and R24 are as defined above.
Some of the preferred nitroarylamine colorants encompassed by Formula I wherein A is a nitroarylamine chromophore have the following Formula (XXIV): 
wherein R36 is selected from hydrogen, halogen, C1-C6-alkyl and C1-C6-alkoxy; R37 and R38 are independently selected from hydrogen; C1-C6-alkyl; C3-C6-cycloalkyl; C3-C8-cycloalkyl; C3-C8-cycloalkyl, C2-C6-alkanoyloxy; aryl and 
Some of the preferred colorants encompassed by Formula I wherein A is a perinone chromophore correspond to Formulae XXV-XXIX: 
wherein R39 is hydrogen or 1-4 groups selected from C1-C6-alkyl, C1-C6-alkoxy, amino, CO2X, C1-C6-alkylamino, C3-C8-cycloalkylamino, arylamino, arylthio, hereroarylthio and 
wherein L7 is selected from xe2x80x94Sxe2x80x94, xe2x80x94Oxe2x80x94 and xe2x80x94NHxe2x80x94, with the provision that one to four xe2x80x94CO2X groups be present.
Preferred colorants of Formula I containing the 2,5-diarylamino terephthalate chromophore have Formula XXX 
wherein R40 is hydrogen or xe2x80x94CO2X or represents 1-3 groups selected from C1-C6-alkyl, C1-C6-alkoxy, halogen, and xe2x80x94NHC2-C6-alkanoylamino.
The preferred photopolymerizable colorant compounds of the present invention are those of Structures I and II where X and Y, respectively, are selected from xe2x80x94CH2CH2OQ, xe2x80x94CH2CH(CH3)OQ, xe2x80x94(CH2CH2O)2-3xe2x80x94CH2CH2OQ, xe2x80x94CH2C(CH3)2CH2OQ, and xe2x80x94CH2xe2x80x94C6H10xe2x80x94CH2OQ, and A is an anthraquinone, anthrapyridone or 2,5-diarylaminoterephthalate chromophore residue.
The photopolymerizable colorants having Formula I and II where X and Y are the photopolymerizable p-vinylbenzyl groups radical having the formula xe2x80x94CH2xe2x80x94C6H4-p-C(R2)xe2x95x90CH2 are prepared in general by reacting colored acidic compounds having Formulae III and IV with a 4-chloro-methylstyreneV, respectively, as follows: 
wherein A, n, R and R2 are as defined previously, to produce colored compounds VI and VII. The reactions of the colored acidic compounds having Formulae III and IV with the 4-chloromethylstyrenes V are carried out in the presence of a polar aprotic solvent such as N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAC), sulfolane, etc. in the presence of one or more bases such as an alkali metal carbonate, an alkali metal bicarbonate, a trialkylamine, a cyclic nitrogen compounds such as 1,8-diazabicyclo [5.4.0]undec-7-ene (PBU), 1,5-diazabicyclo [4.3.0]non-5-ene (DBN), and the like. The reaction may under some reaction conditions be facilitated by the presence of a catalytic amount of an alkali metal bromide, alkali metal iodide and/or a conventional phase transfer catalysts, e.g., a tetraalkylammonium halide such as a chloride or bromide. The reactions are usually carried out between about 50xc2x0 C. to about 150xc2x0 C., preferably from about 90xc2x0 C. to about 125xc2x0 C.
The photopolymerizable dyes having Formulae I and II, where X and Y are xe2x80x94R1xe2x80x94Oxe2x80x94Q are, in general, prepared by first reacting colored acidic acidic compounds having Formulae III and IV with an alkylating agent containing one or more hydroxy groups having Formula VIII as follows: 
wherein A, n, R and R1 are as defined previously and Z is halogen, to produce an intermediate hydroxy compound IX and X. Reaction conditions used for preparing compounds IX and X are those described in the preparation of VI and VII above. Although intermediate hydroxy compounds IX and X where R1 is xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CH2CH(CH3)xe2x80x94 may be prepared as described above by using the corresponding 2-bromo- or chloro-alkanol, the preferred route uses ethylene or propylene carbonate which avoids the use of toxic haloalkanols according to the following equations: 
wherein Rxe2x80x2 is hydrogen or methyl, to produce hydroxyalkyl derivatives XI and XII. These reactions are facilitated by the presence of catalytic amounts of alkali halides, teraalkylammonium halides or tetraalkylammonium hydroxides. The reactions may be carried out by heating the intermediate colored diacids III and IV with at least molar equivalent amounts of alkylene carbonate. Excess alkylene carbonate also may be useful as the solvent or a co-solvent for the reaction. In particular, ethylene and propylene glycol have been found to be effective co-solvents for the preparation of XI and XII. Compounds IX and X (or XI and XII) are then acylated with one of acylating agents Ib through IXb described above to introduce the desired Q groups to prepare photopolymerizable compounds having Formulae I and II. Q groups Ia-IXa are introduced by reacting hydroxy compounds IX and X with acylating agents Ib-IXb, respectively.
Intermediate colored acidic compounds III and IV are disclosed in U.S. Pat. Nos. 3,689,501; 3,816,392; 4,359,570; 4,403,092; 4,617,373; 4,740,581; 4,745,173; 4,804,719; 4,892,922; 5,030,708; 5,102,980; 5,194,571; 5,274,072; 5,281,659; 5,372,864; 5,962,557 and WO 98/23690, wherein particularly useful diacidic intermediate colorants are disclosed.
The azo dyes above which correspond to Formula XIII and Formula XIV may be prepared by reacting azo dyes containing one to four carboxy groups or one to four 1H-1,2,4-triazol-3-ylthio groups, respectively, to incorporate the photopolymerizable groups as described above. Alternatively, the photopolymerizable groups may be incorporated into the diazotiazable amine and/or coupler portion prior to the synthesis of the azo dyes of Formula XIII and XIV.
Typical aromatic amine coupling components(HZ) which contain photopolymerizable groups and are useful in preparing colorants of Formula XIII have the following structures: 
Typical aromatic amine coupling components (HZ1) which contain copolymerizable groups and are useful in preparing colorants of Formula XIV have the following structures: 
In the structures for coupling components HZ and HZ1 above, R15, R16, R18, R19, R20, R24, X and Y have the meaning previously ascribed to them.
Colorants of Formula XV, XVII and XVIII which correspond to colorants containing the methine, 3-aryl-2,5-dioxypyrroline and 3-aryl-5-dicyanomethylene-2-oxypyrroline chromophores, respectively, may be prepared by reacting the intermediate aromatic moiety R25H, as defined previously, which contains one or more photopolymerizable groups with either (a) Vilsmeier complex (e.g., from POCl3/DMF), followed by reaction with the active methylene compound, 
to produce colorants of Formula XV, XVII, and XVIII, respectively, wherein R16xe2x80x2 is hydrogen. Compounds of Formula XVII and XVIII, wherein R16 is hydrogen, can be further reacted to introduce photopolymerizable groups if desired.
A third alternative preparative method for azo colorants having Formula XIII and XIV involves the reaction of electron rich coupler precursors containing at least one xe2x80x94CO2H or 1(H)-1,2,4-triazolyl-3-ylthio group, respectively, with hydroxyalkylating agents to introduce xe2x80x94CO2xe2x80x94R1xe2x80x94OH and 
groups. These couplers then are reacted with the desired diazonium salts to produce azo dye containing the hydroxy groups which are then reacted further to introduce the photopolymerizable Q groups into the final colorant. Similarly, this method may be employed in the preparation of the colorants having Formulae XV, XVI and XVII by reacting the acidic colored intermediates containing the methine, 3-aryl-2,5-dioxypyrroline or 3-aryl-5-dicyano methylene-2-oxypyrroline chromophores, respectively, to introduce the photopolymerizable group after the chromophore is formed.
As is known to those skilled in the art, the 1(H)-1,2,4-triazolyl moiety of Formula II is a mixture of isomers having the structures: 
but that the isomer shown in Formula II probably predominates.
Colorant Examples
The copolymerizable dye compounds provided by the present invention and the preparation thereof are further illustrated by the following examples.